US9580556B2 - DPP with branched alkyl-chain or (and) fused thiophene with branched alkyl-chain and the related designing strategy to increase the molecular weight of their semi-conducting copolymers - Google Patents

DPP with branched alkyl-chain or (and) fused thiophene with branched alkyl-chain and the related designing strategy to increase the molecular weight of their semi-conducting copolymers Download PDF

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US9580556B2
US9580556B2 US14/968,168 US201514968168A US9580556B2 US 9580556 B2 US9580556 B2 US 9580556B2 US 201514968168 A US201514968168 A US 201514968168A US 9580556 B2 US9580556 B2 US 9580556B2
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substituted
polymer
unsubstituted
bis
thiophene
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US20160222167A1 (en
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Mingqian He
James Robert Matthews
Weijun Niu
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Corning Inc
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Corning Inc
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Priority to US14/968,168 priority Critical patent/US9580556B2/en
Priority to CN201680013966.6A priority patent/CN107406585B/zh
Priority to EP16704751.3A priority patent/EP3250624A1/en
Priority to JP2017540154A priority patent/JP6875991B2/ja
Priority to KR1020177024090A priority patent/KR102471602B1/ko
Priority to PCT/US2016/015264 priority patent/WO2016123286A1/en
Priority to TW105102900A priority patent/TWI725952B/zh
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Definitions

  • compositions including heterocyclic organic compounds More specifically, described herein are fused thiophene compounds, methods for making them, and uses thereof.
  • Highly conjugated organic materials are currently the focus of great research activity, chiefly due to their interesting electronic and optoelectronic properties. They are being investigated for use in a variety of applications, including field effect transistors (FETs), thin-film transistors (TFTs), organic light-emitting diodes (OLEDs), electro-optic (EO) applications, as conductive materials, as two photon mixing materials, as organic semiconductors, and as non-linear optical (NLO) materials.
  • FETs field effect transistors
  • TFTs thin-film transistors
  • OLEDs organic light-emitting diodes
  • EO electro-optic
  • Highly conjugated organic materials may find utility in devices such as RFID tags, electroluminescent devices in flat panel displays, and in photovoltaic and sensor devices.
  • Oligomers and polymers of fused thiophenes such as oligo- or poly(thieno[3,2-b]thiophene (2) and oligo- or poly(dithieno[3,2-b:2′-3′-d]thiophene) (1):
  • fused thiophene-based materials have also been suggested for use in electronic and optoelectronic devices, and have been shown to have acceptable conductivities and non-linear optical properties.
  • unsubstituted fused thiophene-based materials tend to suffer from low solubility, marginal processability and oxidative instability.
  • fused thiophene-based materials having acceptable solubility, processability and oxidative stability.
  • compositions including heterocyclic organic compounds such as fused thiophene compounds, methods for making them, and uses thereof.
  • the compositions and methods described herein possess a number of advantages over prior art compositions and methods.
  • the substituted fused thiophene compositions described herein may be made to be more soluble and processable than the analogous unsubstituted thiophene compositions.
  • Polymers and oligomers including the fused thiophene moieties described herein may be processable using conventional spin-coating operations.
  • the compositions described herein may be made with substantially no ⁇ -H content, greatly improving the oxidative stability of the compositions.
  • a first aspect comprises a polymer comprising the repeat unit of formula 1′ or 2′:
  • n and m may be integers, greater than or equal to one;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 may be, independently, hydrogen, substituted or unsubstituted C 4 or greater alkyl, substituted or unsubstituted C 4 or greater alkenyl, substituted or unsubstituted C 4 or greater alkynyl, or C 5 or greater cycloalkyl;
  • a, b, c, and d, independently, may be integers greater than or equal to 3;
  • e and f may be integers greater than or equal to zero;
  • X and Y are, independently a covalent bond, an optionally substituted aryl group, an optionally substituted heteroaryl, an optionally substituted fused aryl or fused heteroaryl group, an alkyne or an alkene; and
  • a and B may be, independently, either S or O, with the provis
  • m is from 1 to 1000.
  • a and B are O.
  • f is 1 and e is 1.
  • f is 1 and e is 0.
  • either R 1 , R 2 , R 3 , and R 4 , or R 5 , R 6 , R 7 , and R 8 are an optionally substituted alkyl group comprising from 8 to 40 carbon atoms.
  • all of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are an optionally substituted alkyl group comprising from 8 to 40 carbon atoms.
  • each of R 1 , R 2 , R 3 , R 4 , R 5 , and R 7 is an optionally substituted alkyl group comprising from 8 to 40 carbon atoms and R 6 and R 8 each are hydrogen.
  • each of R 5 , R 6 , R 7 , R 8 , R 1 , and R 3 is an optionally substituted alkyl group comprising from 8 to 40 carbon atoms and R 2 and R 4 each are hydrogen.
  • the present disclosure also relates, in various embodiments, to a compound, comprising the formula 3′ or 4′
  • each W may be, independently, hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, or vinyl ether, or a substituted or unsubstituted tri-alkyl tin or a boronic ester group or alternative group useful for Suzuki or Stille coupling.
  • the present disclosure also relates, in various embodiments, to a method of making a polymer comprising a substituted fused thiophene.
  • the method of making the polymer may be carried out by reacting a diketopyrrolopyrrole (DPP)-based monomer comprising a moiety of structure 6′ with a fused thiophene compound 3′ or 4′, optionally in the presence of a metal catalyst,
  • DPP diketopyrrolopyrrole
  • the reacting fused thiophene 3′ or 4′ comprises a ditin or diboron-based reactive structure.
  • fused thiophene ditin or diboron may comprise a moiety of structure 7′ or 8′:
  • each R 1 , R 2 , R 3 , R 4 , a, b, Y, e, and n are as defined above for 1′ and 2′, and W′ may be a substituted or unsubstituted tri-alkyl tin or boronic ester group or alternative group useful for Suzuki or Stille coupling.
  • FIG. 1 shows a reaction scheme for forming fused thiophene with branched alkyls.
  • FIG. 4 describes the reaction scheme for coupling bis-tin-substituted FT4 to 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4(2H, 5H)-dione (bis-bromothienyl-DC2BC8C10DPP) via a palladium-catalyzed Stille-type coupling.
  • FIG. 5 illustrates a reaction scheme for coupling a bis-tin-substituted FT4 to 3,6-bis(5-bromothiophen-2-yl)-2,5-dihexadecylpyrrolo[3,4-c]pyrrole-1,4(2H, 5H)-dione (bis-bromothienyl-DC16DPP) via a palladium-catalyzed Stille-type coupling.
  • FIG. 6 illustrates a reaction scheme for coupling a bis-tin-substituted FT4 to bis-bromothienyl-DC16DPP via a palladium-catalyzed Stille-type coupling.
  • FIG. 7 describes a reaction scheme for forming a monomer 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(6-octylhexadecyl)pyrrolo[3,4-c]pyrrole-1,4(2H, 5H)-dione (bis-bromothienyl-DC6BC8C10DPP).
  • FIG. 8 illustrates a reaction scheme for forming 2,6-bis-trimethylstannyl-3,7-bis(5-octylpentadecyl)thieno[3,2-b]thieno[2′,3′:4,5]thieno[2,3-d]thiophene (bis-trimethylstannyl-DC5BC8C10FT4) according to one embodiment.
  • FIG. 9 illustrates a reaction scheme for coupling bis-tin-substituted FT4 to bis-bromothienyl-DC6BC8C10DPP via a palladium-catalyzed Stille-type coupling.
  • FIG. 10 illustrates a reaction scheme for forming a monomer 2,6-bis(5-trimethylstannylthiophen-2-yl)-3,7-bis(5-octylpentadecyl)thieno[3,2-b]thieno[2′,3′:4,5]thieno[2,3-d]thiophene (DSnTDC5BC8C10FT4).
  • FIG. 11 illustrates a reaction scheme for coupling bis-tin-substituted FT4 to bis-bromothienyl-DC6BC8C10DPP via a palladium-catalyzed Stille-type coupling.
  • Ranges may be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
  • alkyl group as used herein may be a branched or unbranched saturated hydrocarbon group of 1 to 40 carbon atoms (or with a number of carbon atoms as defined by the nomenclature C ⁇ -C ⁇ , where ⁇ and ⁇ are a numerical values with ⁇ ), such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, decyl, or tetradecyl, and the like.
  • the alkyl group may be substituted or unsubstituted.
  • unsubstituted alkyl group is defined herein as an alkyl group composed of just carbon and hydrogen.
  • substituted alkyl group is defined herein as an alkyl group with one or more hydrogen atoms substituted with a group including, but not limited to, an aryl group, cycloalkyl group, aralkyl group, an alkenyl group, an alkynyl group, an amino group, an ester, an aldehyde, a hydroxyl group, an alkoxy group, a thiol group, a thioalkyl group, or a halide, an acyl halide, an acrylate, or a vinyl ether.
  • the alkyl groups may be an alkyl hydroxy group, where any of the hydrogen atoms of the alkyl group are substituted with a hydroxyl group.
  • alkyl group as defined herein also includes cycloalkyl groups.
  • cycloalkyl group as used herein is a non-aromatic carbon-based ring composed of at least three carbon atoms, and in some embodiments from three to 20 carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • the term cycloalkyl group also includes a heterocycloalkyl group, where at least one of the carbon atoms of the ring may be substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus.
  • aryl group may be any carbon-based aromatic group, fused carbon-based aromatic group, including, but not limited to, benzene, naphthalene, etc.
  • aryl group also includes “heteroaryl group,” meaning an aromatic ring composed of at least three carbon atoms that has at least one heteroatom incorporated within the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus.
  • the aryl group may be substituted or unsubstituted.
  • the aryl group may be substituted with one or more groups including, but not limited to, alkyl, alkynyl, alkenyl, aryl, halide, nitro, amino, ester, ketone, aldehyde, hydroxy, carboxylic acid, or alkoxy as defined herein.
  • the term “aryl group” may be limited to substituted or unsubstituted aryl and heteroaryl rings having from three to 30 carbon atoms.
  • aralkyl as used herein may be an aryl group having an alkyl group as defined above attached to the aryl group.
  • An example of an aralkyl group may be a benzyl group.
  • alkenyl group is defined as a branched or unbranched hydrocarbon group of 2 to 40 carbon atoms and structural formula containing at least one carbon-carbon double bond.
  • alkynyl group is defined as a branched or unbranched hydrocarbon group of 2 to 40 carbon atoms and a structural formula containing at least one carbon-carbon triple bond.
  • conjugated group is defined as a linear, branched or cyclic group, or combination thereof, in which p-orbitals of the atoms within the group are connected via delocalization of electrons and wherein the structure may be described as containing alternating single and double or triple bonds and may further contain lone pairs, radicals, or carbenium ions.
  • Conjugated cyclic groups may comprise one of or both aromatic and non-aromatic groups, and may comprise polycyclic or heterocyclic groups, such as diketopyrrolopyrrole. Ideally, conjugated groups are bound in such a way as to continue the conjugation between the thiophene moieties they connect. In some embodiments, “conjugated groups” may be limited to conjugated groups having three to 30 carbon atoms.
  • each of the combinations A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D.
  • any subset or combination of these may be also specifically contemplated and disclosed.
  • the sub-group of A-E, B-F, and C-E are specifically contemplated and should be considered disclosed from disclosure of A, B, and C; D, E, and F; and the example combination A-D.
  • This concept applies to all aspects of this disclosure including, but not limited to, steps in methods of making and using the disclosed compositions.
  • steps in methods of making and using the disclosed compositions may be understood that each of these additional steps may be performed with any specific embodiment or combination of embodiments of the disclosed methods, and that each such combination may be specifically contemplated and should be considered disclosed.
  • fused thiophene moieties described herein are substituted with optionally substituted alkyl groups at the ⁇ -positions of the fused thiophene ring system.
  • an ⁇ -position of a fused thiophene ring system may be a non-fused carbon center that may be directly adjacent to the sulfur of a fused thiophene, while a ⁇ -position may be a non-fused carbon center that may be separated from the sulfur of the fused thiophene by an ⁇ -position.
  • the ⁇ -positions are shown as being connected to the rest of the composition, while the ⁇ -positions are substituted with R 1 , R 2 , R 3 , R 4 linked to the ⁇ -positions by alkyl chains.
  • One aspect comprises a polymer comprising a repeat unit of formula 1′ or 2′:
  • n and m may be integers, greater than or equal to one;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 may be, independently, hydrogen, substituted or unsubstituted C 4 or greater alkyl, substituted or unsubstituted C 4 or greater alkenyl, substituted or unsubstituted C 4 or greater alkynyl, or C 5 or greater cycloalkyl;
  • a, b, c, and d, independently, may be integers greater than or equal to 3;
  • e and f may be integers greater than or equal to zero;
  • X and Y are, independently a covalent bond, an optionally substituted aryl group, an optionally substituted heteroaryl, an optionally substituted fused aryl or fused heteroaryl group, an alkyne or an alkene; and
  • a and B may be, independently, either S or O, with the provis
  • At least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 may be a substituted or unsubstituted C 4 or greater alkyl group.
  • at least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 may be an unsubstituted C 4 or greater alkyl group.
  • the unsubstituted C 4 or greater alkyl group may be a straight-chain alkyl group (e.g.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 comprises a substituted C 4 or greater alkyl.
  • At least one of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 may be substituted with amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, or vinyl ether moieties or any combination of two or more of these.
  • the selection of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 will depend on the end use of the fused thiophene moiety-containing composition.
  • each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 is, independently, a substituted or unsubstituted C 4 or greater alkyl. In some embodiments, each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 is, independently, a substituted or unsubstituted C 6 or greater alkyl.
  • R 1 and R 3 are hydrogen
  • R 4 and R 2 are each a substituted or unsubstituted C 6 or greater alkyl
  • each R 5 , R 6 , R 7 , and R 8 is, independently, a substituted or unsubstituted C 8 or greater alkyl
  • R 5 and R 7 are hydrogen
  • R 6 and R 8 are each a substituted or unsubstituted C 6 or greater alkyl
  • each R 1 , R 2 , R 3 , and R 4 is, independently, a substituted or unsubstituted C 8 or greater alkyl.
  • n is an integer of 1 or greater. In some embodiments, n is an integer from 1 to 4, or 1 to 3. In one aspect, m may be from 1 to 10,000, 1 to 9,000, 1 to 8,000, 1 to 7,000, 1 to 6,000, 1 to 5,000, 1 to 4,000, 1 to 3,000, 1 to 2,000, 1 to 1,000, 1 to 500, 1 to 250, 1 to 100, 1 to 50, 1 to 25, 1 to 10, 25 to 1000, 25 to 500, 25 to 250, 50 to 1000, 50 to 500, or 50 to 250. In some embodiments, at least one of A or B is O. In other embodiments, at least one of A or B is S.
  • each X and Y is individually a conjugated group.
  • the conjugated group is a substituted or unsubstituted aryl, heteroaryl, or a double or triple bond.
  • each X and Y is individually substituted or unsubstituted aryl or heteroaryl.
  • each X and Y is individually substituted or unsubstituted heteroaryl.
  • each X and Y is individually substituted or unsubstituted thiophene or fused thiophene.
  • each X and Y is individually an unsubstituted thiophene.
  • each X and Y is individually one of:
  • each R 9 and R 10 is independently, hydrogen, substituted or unsubstituted alkyl having from 1 to 30 carbon atoms, substituted or unsubstituted alkenyl having from 1 to 30 carbon atoms, substituted or unsubstituted alkynyl, having from 1 to 30 carbon atoms, substituted or unsubstituted aryl having from 4 to 30 carbon atoms, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl.
  • at least one of R 9 , and R 10 may be an alkyl group comprising from 2 to 30 carbon atoms.
  • At least one of R 9 , and R 10 comprises a substituted or unsubstituted alkyl.
  • one or more substituents may be selected from amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, or vinyl ether moieties or any combination of two or more of these.
  • the fused thiophene moieties described in 1′ and 2′ may have any number of fused rings above 3.
  • the methods described herein permit the construction of fused thiophene moieties having any desired number of rings.
  • n may be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15.
  • An unexpected advantage of the embodied compounds as shown in structures 1′ and 2′ is that the presence of at least four long alkyl chains on the polymer, with at least two alkyl chains with branching points at the C 4 position or greater provide improved mobility and processability properties.
  • one or both of the fused thiophene unit and the DPP unit contain branched alkyl chains where the branch point is at least four carbons away from the polymer backbone.
  • the multiple branched side chains in one polymer repeat unit significantly increase the solubility of the polymer, allowing for the polymer to be synthesized with an increased molecular weight without sacrificing other device properties, such as solution processability and ⁇ - ⁇ stacking.
  • the embodied polymers shown in 1′ and 2′ have higher field effect hole mobility than current high performance polymers, such as shown in the below structure (from U.S. application Ser. No. 13/665,055, filed Oct. 31, 2012, herein incorporated by reference):
  • both FT4 units and DPP units in the polymers, wherein both groups contain two large alkyl chains, with at least two alkyl chains with branching points at the C 4 position or greater.
  • the embodied polymers provide superior properties because 1) since all branched alkyl chains are at least four carbons away from the main polymer backbone, there is no or very low steric effect from them to cause the twisting of the original planarity of the polymer backbone, which would interfere with the ⁇ -stacking of the polymer backbones, and 2) the existence of four large, nonpolar branched side chains in one polymer repeat unit significantly increases the solubility of these polymers and thus allow for an increase in the molecular weight of the polymers, which may result in an enhanced mobility over current high performance polymers.
  • the fused thiophenes may be in liquid form at temperatures as low as 10° C., 5° C., 0° C., ⁇ 5° C., or ⁇ 10° C.
  • Previously made polymers generally have limited solubility in various solvents and may be difficult to process, e.g., when preparing printed electronics, without negatively impacting electronic performance.
  • the embodied FT4 monomers may satisfy these requirements since branched side-chain FT4 may be used to construct a larger conjugation system with less worry about solubility limitations.
  • R 1 R 2 CH(CH 2 ) a+1 and R 3 R 4 CH(CH 2 ) b+1 may be identical alkyl groups and/or R 5 R 6 CH(CH 2 ) c+1 and R 7 R 8 CH(CH 2 ) d+1 may be identical alkyl groups.
  • R 1 R 2 CH(CH 2 ) a+1 and R 3 R 4 CH(CH 2 ) b+1 and/or R 5 R 6 CH(CH 2 ) c+1 and R 7 R 8 CH(CH 2 ) d+1 are identical, regioregular polymers may be easily constructed because the problems of regioselectivity (i.e. head-to-tail vs.
  • R 1 R 2 CH(CH 2 ) a+1 and R 3 R 4 CH(CH 2 ) b+1 and/or R 5 R 6 CH(CH 2 ) c+1 and R 7 R 8 CH(CH 2 ) d+1 may be different.
  • one set of “R” groups e.g., R 1 R 2
  • R 3 R 4 may be at least four carbons in size
  • the other set of “R” groups e.g., R 3 R 4
  • all R 1 -R 8 while optionally different, may be at least four carbons in length.
  • X and Y may be attached to the ⁇ -position of the fused thiophene moiety.
  • each X and Y may independently have one of the structures:
  • each X or Y may independently be one of the structures:
  • the polymer may be chosen from those of formula 1A′ or 2A′ below:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , A, and B are as defined above for formulas 1′ and 2′.
  • the thiophene groups are unsubstituted:
  • the polymer compound may be chosen from those of formula 1AA′ or 2AA′ below:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , A, and B are as defined above for formulas 1′ and 2′.
  • the thiophene groups are unsubstituted:
  • a, b, c, or d independently, may be integers of 3 or greater.
  • at least one of X and Y may be a substituted or unsubstituted thiophene group.
  • compositions disclosed herein may comprise at least one moiety comprising the formula 1B′, 2B′, 1C′, or 2C′:
  • each Q 1 , Q 2 , Q 3 , and Q 4 may be, independently, an optionally substituted linear (i.e., unbranched) alkyl, optionally substituted linear alkenyl, or optionally substituted linear alkynyl.
  • a, b, c, or d independently, may be integers greater than 3, 4, 5, or 6.
  • at least one of X and Y may be a substituted or unsubstituted thiophene group.
  • Q 1 , Q 2 , Q 3 , and Q 4 independently, may be substituted or unsubstituted linear alkyl groups.
  • a compound may comprise the formula 7′ or 8′
  • a, b, e, n, R 1 , R 2 , R 3 , R 4 , and Y are as defined above for formulas 1′ and 2′, and W may be, independently, hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, aryl, cycloalkyl, aralkyl, amino, ester, aldehyde, hydroxyl, alkoxy, thiol, thioalkyl, halide, acyl halide, acrylate, or vinyl ether, or a substituted or unsubstituted tri-alkyl tin or a boronic ester group or alternative group useful for Suzuki or Stille coupling.
  • a and b independently, may be integers greater than 3.
  • the compound may be chosen from those of formula 7A′ or 8A′ below:
  • the thiophene groups are unsubstituted:
  • Another aspect comprises methods of making the compounds, monomers, and polymers described herein.
  • Methods of making fused thiophene-based structures may be found in U.S. application Ser. No. 13/665,055, filed Oct. 31, 2012, U.S. application Ser. No. 12/905,667, filed Oct. 15, 2010, U.S. application. Ser. No. 12/935,426, filed Sep. 29, 2010, U.S. application Ser. No. 12/851,998, filed Aug. 6, 2010, U.S. application. Ser. No. 13/397,021, filed Feb. 15, 2012, U.S. application Ser. No. 13/660,529, filed Oct. 25, 2012, and U.S. Pat. Nos. 7,705,108, 7,838,623, 8,389,669, 7,893,191, 8,349,998, 7,919,634, 8,278,410, and 8,217,183, all of which are incorporated herein by reference in their entirety.
  • compounds comprising the moiety 1′ or 2′ may be produced by reacting a compound comprising 6′ with a compound comprising 7′ or 8′.
  • the method for making a compound, such as 1′ or 2′ may be carried out by providing a diketopyrrolopyrrole (DPP) based monomer comprising a moiety of structure 6′:
  • DPP diketopyrrolopyrrole
  • A, B, c, d, X, f, R 5 , R 6 , R 7 , and R 8 are as listed above for 1′ and 2′ and Z may be a halogen, such as Cl, Br, I, for example.
  • c and d are each independently, integers greater than or equal to 5.
  • the method of making the compound may be further carried out by providing a fused thiophene ditin or diboron compound comprising a moiety of structure 7′′ or 8′′:
  • W′ may be tri-alkyl tin, such as Sn(Alk) 3 , where “Alk” is an optionally substituted alkyl group, or a boronic ester group, such as Alk-B(OAlk) 2 , where each “Alk” is an optionally substituted alkyl group.
  • Each W′ may also be an alternative group, known or unknown, useful for Suzuki or Stille coupling.
  • Compounds comprising the moiety 1B′ or 2B′ may be produced by reacting a compound comprising 6′ and 7B′ or 8B′.
  • the method for making a compound, such as 1B′ or 2B′ may be carried out by providing a diketopyrrolopyrrole (DPP) based monomer comprising a moiety of structure 6′ and a fused thiophene ditin or diboron compound comprising a moiety of structure 7B′ or 8B′:
  • DPP diketopyrrolopyrrole
  • W′ may be tri-alkyl tin, such as Sn(Alk) 3 , where “Alk” is an optionally substituted alkyl group, or a boronic ester group, such as Alk-B(OAlk) 2 , where each “Alk” is an optionally substituted alkyl group.
  • Each W′ may also be an alternative group, known or unknown, useful for Suzuki or Stille coupling.
  • compounds comprising the moiety 1C′ or 2C′ may be produced by reacting a compound comprising 6C′ and 7′ or 8′.
  • the method for making a compound, such as 1C′ or 2C′ may be carried out by providing a diketopyrrolopyrrole (DPP) based monomer comprising a moiety of structure 6C′ below and reacting this monomer with a compound of 7′ or 8′ as defined above.
  • DPP diketopyrrolopyrrole
  • Z, X, f, A, and B are as defined in 6′ and Q 3 and Q 4 are as defined in 1C′ and 2C′.
  • the methods may be further carried out by forming a polymer in presence of a metal catalyst.
  • the metal catalyzed reaction may be a Stille-type reaction or Suzuki coupling reaction.
  • compounds comprising the moiety 1′ or 2′ may be produced through a series of synthetic steps.
  • the fused thiophene core may be synthesized and brominated as described herein.
  • the dibromo-fused thiophene may then be sequentially reacted with butyllithium and trimethyltinchloride to form the bis-tin-substituted fused thiophene as shown in FIG. 1 .
  • the formation of the dipyrrolopyrole moiety may be done via the reaction scheme shown in Tieke et al., Beilstein, J. O RG . C HEM . 830 (2010), herein incorporated by reference in its entirety, and may be described in FIG.
  • the fused thiophene moiety and the dipyrrolopyrrole moiety may be combined to form 1′ or 2′ via any standard coupling reaction.
  • the fused thiophene moiety and the dipyrrolopyrrole moiety may be combined via a Stille-type coupling reaction as shown in FIG. 3 .
  • the reaction in FIG. 3 The reaction in FIG.
  • Fused thiophene and oxidized fused thiophene oligomers and polymers may be prepared using methodologies similar to those used in making oligo- and poly(thiophenes) described above.
  • ⁇ , ⁇ ′-dihydro fused thiophene moieties may be oxidatively oligomerized or polymerized using iron (III) compounds (e.g., FeCl 3 , Fe(acac) 3 ), or may be brominated and coupled in an organomagnesium mediated reaction.
  • fused thiophene moieties and oxidized fused thiophene moieties described herein may be incorporated into other conjugated polymers such as, for example phenylene, vinylene, and acetylene copolymers, using coupling reactions familiar to the skilled artisan.
  • the fused thiophene moieties and oxidized fused thiophene moieties described herein may be incorporated into other main chain and side chain polymers using techniques known in the art. It is contemplated that the fused thiophene compound may be oxidized prior to incorporation into an oligomer or polymer. In the alternative, the fused thiophene compound may be incorporated into the oligomer or polymer followed by oxidation.
  • the reaction vessel and cap are introduced into a nitrogen glovebox, where toluene (10 mL) is added and the cap affixed to the vessel.
  • the vessel is then removed from the glovebox and the reaction microwaved at 160° C. for 2 h.
  • the mixture is cooled to 50° C. before release from the microwave reactor, then poured into a stirring mixture of methanol and acetylacetone (100 mL+100 mL).
  • Hydrochloric acid (1 mL, 35% aq) is added and the mixture is stirred for 16 h.
  • the mixture is filtered and the polymer placed into a glass with glass frit Soxhlet thimble.
  • the polymer is extracted in a Soxhlet apparatus with acetone (250 mL) for 24 h, then hexanes (250 mL) for 24 h.
  • the polymer is then extracted from the Soxhlet apparatus into chloroform (250 mL).
  • the chloroform solution is poured into methanol (400 mL) with rapid stirring, followed by moderate stirring for 20 min.
  • the reaction vessel and cap are introduced into a nitrogen glovebox, where toluene (10 mL) is added and the cap affixed to the vessel.
  • the vessel is then removed from the glovebox and the reaction microwaved at 160° C. for 2 h.
  • the mixture is cooled to 50° C. before release from the microwave reactor, then poured into a stirring mixture of methanol and acetylacetone (100 mL+100 mL).
  • Hydrochloric acid (1 mL, 35% aq) is added and the mixture stirred for 16 h.
  • the mixture is filtered and the polymer placed into a glass with glass frit Soxhlet thimble.
  • the polymer is extracted in a Soxhlet apparatus with acetone (250 mL) for 24 h.
  • the polymer is soluble in hexane so no hexane extraction is carried out.
  • the polymer is extracted into chloroform and the chloroform solution is poured into methanol (400 mL) with rapid stirring, followed by moderate stirring for 20 min.
  • the reaction vessel and cap are introduced into a nitrogen glovebox, where toluene (20 mL) is added and the cap affixed to the vessel.
  • the vessel is then removed from the glovebox and the reaction microwaved at 160° C. for 2 h.
  • the mixture is cooled to 50° C. before release from the microwave reactor, then poured into a stirring mixture of methanol and acetylacetone (100 mL+100 mL).
  • Hydrochloric acid (1 mL, 35% aq) is added and the mixture stirred for 16 h.
  • the mixture is filtered and the polymer placed into a glass with glass frit Soxhlet thimble.
  • the polymer is extracted in a Soxhlet apparatus with acetone (250 mL) for 24 h.
  • the polymer is very soluble in hexane so no hexane extraction is carried out.
  • the polymer is extracted into chloroform and the chloroform solution is poured into methanol (400 mL) with rapid stirring, followed by moderate stirring for 20 min.
  • This reaction solution is then allowed to cool down and was poured into ice water, and the resulting suspension is stirred at room temperature for 1 h.
  • Chloroform 400 mL is used to extract the product.
  • 200 mL of hexane is used to extract the aqueous residue.
  • the organic layers are combined and washed by water twice and then dried over anhydrous magnesium sulfate. All solvents are removed and the resulting dark reddish oily product is redissolved in hexane and shot path silica chromatography is carried out using 1:1 hexane/methylene chloride as the eluent.
  • Solvents hexane/methylene chloride are removed to yield a dark red waxy solid that is dissolved in about 80 mL of acetone with gentle heating. The solution is then cooled and kept at ⁇ 18° C. for three hours where a dark red solid forms in the bottom. Solvent acetone is removed by decanting and the residual pure dark reddish solid product, 3,6-bis(5-bromothiophen-2-yl)-2,5-bis(6-octylhexadecyl)pyrrolo[3,4-c]pyrrole-1,4(2H, 5H)-dione (DTDC6BC8C10DPP), is dried under vacuum overnight (6.18 g, 76%).
  • dicarboxylic acid-DC5BC8C10FT4 (6.89 g, 6.99 mmol), Cu 2 O (200 mg, 1.40 mmol), glycine (157 mg, 2.10 mmol), and 60 mL of tetraethyleneglycol dimethylether are added. Under nitrogen protection, this stirred solution is heated at 250° C. for four hours. The hot reaction mixture is filtered quickly through a hot frit to remove the copper oxide and other solid residue. After the addition of 250 mL of methanol, the filtrate is cooled in a freezer to yield a grey precipitate.
  • the supernatant liquid is removed by decanting since the solid becomes a liquid quickly at RT.
  • This solid is re-dissolved in 60 mL of hexane and is washed by aqueous 2M HCl (aq) solution (2 ⁇ 150 mL), then is washed by water (2 ⁇ 190 mL).
  • This hexane solution is then dried over anhydrous magnesium sulfate. After a filtration, solvent hexane is removed to yield an oily product.
  • a silica column chromatography is carried out using hexane as the eluent.
  • reaction solution is heated at 120° C. for 2 h.
  • the reaction solution is then cooled to RT and then poured into a stirring mixture of methanol and acetylacetone (100 mL+20 mL).
  • Hydrochloric acid (1 mL, 35% aq) is added and the mixture stirred for 16 h.
  • the mixture is filtered and the polymer placed into a Soxhlet thimble.
  • the polymer is extracted in a Soxhlet apparatus with acetone (250 mL) for 24 h.
  • the polymer is very soluble in hexane so no hexane extraction is carried out.
  • This reaction solution is quenched by adding water and subsequently adding aqueous HCl solution into the flask, followed by 300 mL of hexane. After vigorous shaking, the organic layer is collected. The organic portion thus collected is then washed with water and dried over anhydrous sodium sulfate. The solvents are removed to yield an oily product. Silica column chromatography is carried out using hexane as the eluent.
  • reaction mixture is then purified by silica column chromatography using hexane as the eluent. Under reduced pressure, solvent hexane is removed to yield a yellowish solid, which is subsequently heated in 30 mL of ethanol at 70° C. with agitation for 20 minutes. After cooling to room temperature, ethanol is removed by decanting to yield a yellowish solid product. This product is then dissolved in ethyl acetate and recrystallized after cooling to room temperature and further cooling in the refrigerator to 4° C.
  • reaction temperature is warmed to ⁇ 12° C. and a Me 3 SnCl solution (1.0 M in THF) (3.54 mL, 3.54 mmol) is then added dropwise.
  • the reaction solution is warmed to room temperature and stirred overnight. This reaction solution is quenched by adding ice-water. After removing most of the THF under reduced pressure, 150 mL of water and 40 mL of hexane are added. After vigorously shaking, the hexane layer is collected, washed by water and then dried over anhydrous sodium sulfate. To this oily product, 30 mL of ethanol is added, followed by washing with hot ethanol (71° C.).
  • DSnTDC5BC8C10FT4 (900 mg, 0.65 mmol, MW 1387.2), DBrTDC6BC8C10DPP (734 mg, 0.65 mmol, MW 1131.4) (synthesized according to the reaction scheme illustrated in FIG. 7 ), tris(dibenzylideneacetone)dipalladium(0) (11.9 mg, 0.013 mmol) and o-tolyl phosphine (15.8 mg, 0.052 mmol).
  • the flask is introduced into a nitrogen glovebox, where chlorobenzene (10 mL) is added and the septa are capped to the flask. The flask is then removed from the glovebox. Under nitrogen protection, the reaction solution is heated at 120° C. in an oil bath for 1 h. The reaction solution is then cooled to RT and poured into a stirring mixture of methanol and acetylacetone (200 mL+200 mL). Hydrochloric acid (2 mL, 35% aq) is added and the mixture stirred for 16 h. The mixture is filtered and the polymer placed into a Soxhlet thimble. The polymer is extracted in a Soxhlet apparatus with acetone (250 mL) for 24 h.
  • the polymers disclosed herein may still exhibit high solubility, e.g., in various organic solvents such as xylene, toluene, tetrahydronaphthalene, cyclooctane, and the like. Moreover, the polymers may be dissolved in such solvents at room temperature or at relatively low temperatures (e.g., about 100° C. or less).
  • OFETs Organic field-effect transistors
  • P2TDC6BC8C10DPP2TDC5BC8C10FT4 ventive
  • PTDC16DPPTDC17FT4 comparative
  • Various parameters of these fabricated devices are measured, including average charge carrier mobility ( ⁇ h ), average current On/Off ratio (I ON /I OFF ), and average threshold voltage (V th ). The results of these tests are presented in Table I below.
  • Such an increased carrier mobility can be achieved while annealing at relatively lower temperatures (e.g., as low as 160° C.), as compared to higher annealing temperatures, which are often necessary and were previously used to improve carrier mobility of known OSC polymers (e.g., 190° C. or greater).
  • polymers disclosed herein may have relatively high molecular weight and/or molecular volume (due to longer side chains), such polymers may still exhibit the unexpected advantage of a decreased ⁇ - ⁇ stacking distance, e.g., these polymers may have improved packing ability.
  • the lamellar spacing and in-plane stacking distance of the deposited inventive and comparative organic films are presented below in Table II.
  • the polymer may benefit from improved planarity and/or reduced twisting, such that the polymer can stack more efficiently (as evidenced by the reduced in-plane stacking distance).
  • the polymers disclosed herein may benefit from the branched side chains in terms of improved solubility, while also exhibiting a good packing ability, which can result in a higher charge carrier mobility.

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US14/968,168 US9580556B2 (en) 2015-01-29 2015-12-14 DPP with branched alkyl-chain or (and) fused thiophene with branched alkyl-chain and the related designing strategy to increase the molecular weight of their semi-conducting copolymers
KR1020177024090A KR102471602B1 (ko) 2015-01-29 2016-01-28 분지형 알킬-사슬 및/또는 분지형 알킬-사슬을 갖는 융합 티오펜을 갖는 dpp 및 이들의 반-도전 공중합체의 분자량을 증가시키는 관련 설계 전략
EP16704751.3A EP3250624A1 (en) 2015-01-29 2016-01-28 Dpp with branched alkyl-chain or (and) fused thiophene with branched alkyl-chain and the related designing strategy to increase the molecular weight of their semi-conducting copolymers
JP2017540154A JP6875991B2 (ja) 2015-01-29 2016-01-28 分岐アルキル鎖を有するｄｐｐまたは（および）分岐アルキル鎖を有する縮合チオフェン、並びにそれらの半導体コポリマーの分子量を増加させるための設計戦略
CN201680013966.6A CN107406585B (zh) 2015-01-29 2016-01-28 具有分枝状烷基链的dpp或/和具有分枝状烷基链的稠合噻吩
PCT/US2016/015264 WO2016123286A1 (en) 2015-01-29 2016-01-28 Dpp with branched alkyl-chain or (and) fused thiophene with branched alkyl-chain and the related designing strategy to increase the molecular weight of their semi-conducting copolymers
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